Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres

ABSTRACT

The present invention relates, firstly, to a cosmetic and/or dermatological composition intended for treating keratin fibers, in particular human keratin fibers and more particularly human hair, comprising, in a support which is suitable for keratin fibers: (a) at least one enzyme of 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme; (b) at least one substantive polymer chosen from the group consisting of: (i) cationic cellulose derivatives; (ii) dimethyldiallylammonium halide homopolymers and copolymers of dimethyldiallylammonium halide and of (meth)acrylic acid; (iii) methacryloyloxyethyltrimethylammonium halide homopolymers and copolymers; (iv) polyquaternary ammonium polymers; (v) vinylpyrrolidone polymers containing cationic units; (vi) mixtures thereof. The present invention also relates to processes for treating keratin fibers, in particular processes for dyeing, permanently reshaping or bleaching the hair using this composition.

[0001] The present invention relates, firstly, to a cosmetic and/ordermatological composition intended for treating keratin fibres, inparticular human keratin fibres and more particularly human hair,comprising, in a support which is suitable for keratin fibres:

[0002] (a) at least one enzyme of 2-electron oxidoreductase type in thepresence of at least one donor for the said enzyme;

[0003] (b) at least one substantive polymer chosen from the groupconsisting of:

[0004] (i) cationic cellulose derivatives;

[0005] (ii) dimethyldiallylammonium halide homopolymers and copolymersof dimethyldiallylammonium halide and of (meth)acrylic acid;

[0006] (iii) methacryloyloxyethyltrimethylammonium halide homopolymersand copolymers;

[0007] (iv) polyquaternary ammonium polymers;

[0008] (v) vinylpyrrolidone polymers containing cationic units;

[0009] (vi) mixtures thereof.

[0010] The present invention also relates to processes for treatingkeratin fibres, in particular processes for dyeing, permanentlyreshaping or bleaching the hair using this composition.

[0011] The present invention relates to an oxidizing compositionintended for treating keratin fibres, comprising at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme and at least one cationic or amphoteric substantivepolymer, as well as to its uses for dyeing, for permanently reshaping orfor bleaching keratin fibres, in particular human hair.

[0012] It is known to dye keratin fibres, and in particular human hair,with dye compositions containing oxidation dye precursors, in particularpara-phenylenediamines, ortho- or para-aminophenols and heterocyclicbases, which are generally referred to as oxidation bases. Oxidation dyeprecursors, or oxidation bases, are colourless or weakly colouredcompounds which, when combined with oxidizing products, can give rise tocoloured compounds and dyes by a process of oxidative condensation.

[0013] It is also known that the shades obtained with these oxidationbases can be varied by combining them with couplers or colour modifiers,the latter being chosen in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

[0014] The variety of compounds used as regards the oxidation bases andthe couplers allows a wide range of colours to be obtained.

[0015] The so-called “permanent” coloration obtained by means of theseoxidation dyes must moreover satisfy a certain number of requirements.Thus, it must have no toxicological drawbacks, it must be able to giveshades of the desired intensity and it must be able to withstandexternal agents (light, bad weather, washing, permanent-waving,perspiration, rubbing).

[0016] The dyes must also be able to cover white hair and, lastly, theymust be as unselective as possible, i.e. they must give the smallestpossible colour differences along the same length of keratin fibre,which may in fact be differently sensitized (i.e. damaged) between itstip and its root.

[0017] The oxidation dyeing of keratin fibres is generally carried outin alkaline medium, in the presence of hydrogen peroxide. However, theuse of alkaline media in the presence of hydrogen peroxide has thedrawback of causing appreciable degradation of the fibres, as well asconsiderable bleaching of the keratin fibres, which is not alwaysdesirable.

[0018] The oxidation dyeing of keratin fibres can also be carried outusing oxidizing systems other than hydrogen peroxide, such as enzymaticsystems. Thus, it has already been proposed to dye keratin fibres, inparticular in patent application EP-A-0,310,675, with compositionscomprising an oxidation dye precursor in combination with enzymes suchas pyranose oxidase, glucose oxidase or uricase, in the presence of adonor for the said enzymes. Although being used under conditions whichdo not result in degradation of the keratin fibres which is comparableto that caused by the dyes used in the presence of hydrogen peroxide,these dye formulations nevertheless lead to colorations which are stillinsufficient, both as regards the homogeneity of the colour distributedalong the fibre (“unison”) and as regards the chromaticity (luminosity),the dyeing power and the resistance to the various aggressive factors towhich the hair may be subjected.

[0019] It is known that the most common technique for obtaining apermanent reshaping of the hair consists, in a first stage, in openingthe keratin —S—S-disulphide (cysteine) bonds using a compositioncontaining a suitable reducing agent (reduction step) followed, afterhaving rinsed the head of hair thus treated, by reconstituting, in asecond stage, the said disulphide bonds by applying to the hair, whichhas been placed under tension beforehand (rollers and the like), anoxidizing composition (oxidation step, also known as the fixing step) soas finally to give to the hair the desired shape. This technique thusmakes it equally possible either to make the hair wavy or to straightenit or to remove its curliness. The new shape given to the hair by achemical treatment such as above is remarkably long-lasting and inparticular resists the action of washing with water or shampoos, asopposed to simple standard techniques for temporary reshaping, such ashairsetting.

[0020] The reducing compositions which may be used in order to carry outthe first step of a permanent-waving operation generally contain, asreducing agents, sulphites, bisulphites, alkylphosphines or, preferably,thiols. Among the thiols, those commonly used are cysteine and thevarious derivatives thereof, cysteamine and the derivatives thereof,thiolactic acid or thioglycolic acid, the salts thereof and the estersthereof, in particular glyceryl thioglycolate.

[0021] As regards the oxidizing compositions needed to carry out thefixing step, use is usually made in practice of compositions based onaqueous hydrogen peroxide, sodium bromate or persalts such as sodiumperborate, which have the drawback of being liable to damage the hair.

[0022] The problem of the technique of the permanent-waving operationsknown to date is that their application to the hair induces long-termadverse changes in the quality of the hair. The essential causes ofthese adverse changes in the quality of the hair are a reduction in itscosmetic properties, such as its sheen and its feel, and degradation ofits mechanical properties, more particularly degradation of itsmechanical strength due to swelling of the keratin fibres during therinsing between the reduction step and the oxidation step, which canalso be reflected by an increase in its porosity. The hair is weakenedand can become brittle during subsequent treatments such as blow-drying.

[0023] The same problem of adverse changes in keratin fibres isencountered during processes for bleaching the hair.

[0024] It is known that the permanent reshaping or bleaching of keratinfibres can also be carried out under milder conditions using oxidizingsystems other than hydrogen peroxide, such as enzymatic systems. Thus,processes for the permanent reshaping or bleaching of keratin fibreshave already been proposed, in particular in patent applicationEP-A-0,310,675, with compositions comprising an enzyme such as pyranoseoxidase, glucose oxidase or uricase, in the presence of a donor for thesaid enzyme. Although being used under conditions which do not result indegradation of the keratin fibres which is comparable to that caused bythe conventional permanent-waving or bleaching processes, theseoxidizing formulations nevertheless lead to results which are stillinsufficient, as regards the curl hold over time, as regards thecompatibility of permanent-waved or bleached hair with subsequenttreatments, as regards the reduction of the mechanical properties of thepermanent-waved hair, in particular the reduction of the porosity of thehair, and as regards the reduction of the cosmetic properties such asthe feel, or alternatively as regards the uniformity of the bleachingalong the keratin fibres.

[0025] The aim of the present invention is to solve the problemsmentioned above.

[0026] The Applicant has discovered, surprisingly, novel compositionscontaining as oxidizing system, at least one enzyme of 2-electronoxidoreductase type in the presence of at least one donor for the saidenzyme and at least one specific substantive polymer which will bedefined in further detail later, which can constitute, in the presenceof oxidation dye precursors (oxidation bases) and optionally couplers,ready-to-use dye formulations which lead to more homogeneous, moreintense and more chromatic colorations without giving rise to anysignificant degradation, these colorations being relatively unselectiveand showing good resistance to the various aggressive factors to whichthe hair may be subjected.

[0027] The Applicant has also discovered, unexpectedly, that the use, ina process for the permanent reshaping of keratin fibres, of an oxidizingcomposition containing, as oxidizing system, at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme and at least one specific substantive polymer, makes itpossible to solve the technical problems mentioned above. In particular,this type of oxidizing composition improves the curl hold obtained overtime, substantially reduces the porosity of permanent-waved hair andimproves the compatibility of permanent-waved hair with respect tosubsequent treatments.

[0028] The Applicant has also discovered, surprisingly, that the use, ina process for bleaching keratin fibres, of an oxidizing compositioncontaining, as oxidizing system, at least one enzyme of 2-electronoxidoreductase type in the presence of at least one donor for the saidenzyme and at least one specific substantive polymer makes it possibleto solve the technical problems mentioned above, in particular toimprove the compatibility of bleached hair with respect to subsequenttreatments. This type of oxidizing composition gives a more uniformbleaching effect on the hair and improves the cosmetic properties, suchas the feel.

[0029] These discoveries form the basis of the present invention.

[0030] The subject of the present invention is thus, firstly, a cosmeticand/or dermatological composition intended for treating keratin fibres,in particular human keratin fibres and more particularly human hair,comprising, in a support which is suitable for keratin fibres:

[0031] (a) at least one enzyme of 2-electron oxidoreductase type in thepresence of at least one donor for the said enzyme,

[0032] (b) at least one substantive polymer chosen from the groupconsisting of:

[0033] (i) cationic cellulose derivatives;

[0034] (ii) dimethyldiallylammonium halide homopolymers and copolymersof dimethyldiallylammonium halide and of (meth)acrylic acid;

[0035] (iii) methacryloyloxyethyltrimethylammonium halide homopolymersand copolymers;

[0036] (iv) polyquaternary ammonium polymers;

[0037] (v) vinylpyrrolidone polymers containing cationic units;

[0038] (vi) mixtures thereof.

[0039] The 2-electron oxidoreductase(s) used in the oxidizingcompositions in accordance with the invention can be chosen inparticular from pyranose oxidases, glucose oxidases, glycerol oxidases,lactate oxidases, pyruvate oxidases and uricases.

[0040] According to the invention, the 2-electron oxidoreductase ispreferably chosen from uricases of animal, microbiological orbiotechnological origin.

[0041] By way of example, mention may be made of uricase extracted fromboar liver, uricase from Arthrobacter globiformis, as well as uricasefrom Aspergillus flavus.

[0042] The 2-electron oxidoreductase(s) can be used in pure crystallineform or in a form diluted in a diluent which is inert with respect tothe said 2-electron oxidoreductase.

[0043] The 2-electron oxidoreductase(s) in accordance with the inventionpreferably represent(s) from 0.01 to 20% by weight approximatelyrelative to the total weight of the composition, and even morepreferably from 0.1 to 5% by weight approximately relative to thisweight.

[0044] According to the invention, the term donor is understood to referto the various substrates also necessary for the functioning of the said2-electron oxidoreductase(s).

[0045] The nature of the donor (or substrate) for the said enzyme variesdepending on the nature of the 2-electron oxidoreductase used. Forexample, as donors for the pyranose oxidases, mention may be made ofD-glucose, L-sorbose and D-xylose; as a donor for the glucose oxidases,mention may be made of D-glucose; as donors for the glycerol oxidases,mention may be made of glycerol and dihydroxyacetone; as donors for thelactate oxidases, mention may be made of lactic acid and its salts; asdonors for the pyruvate oxidases, mention may be made of pyruvic acidand its salts; and lastly, as donors for the uricases, mention may bemade of uric acid and its salts.

[0046] The donor(s) (or substrate(s)) used in accordance with theinvention preferably represent from 0.01 to 20% by weight approximatelyrelative to the total weight of the composition in accordance with theinvention, and even more preferably from 0.1 to 5% approximatelyrelative to this weight.

[0047] The substantive nature (that is to say the ability to bedeposited on the hair) of the polymers used in accordance with theinvention is determined conventionally using the test described byRichard J. Crawford, Journal of the Society of Cosmetic Chemists, 1980,31—(5)—pages 273 to 278 (development by Red 80 acidic dye).

[0048] These substantive polymers may be chosen from those previouslydescribed in the literature, in particular in patent applicationEP-A-0,557,203, from page 4, line 19 to page 12, line 14.

[0049] Among the cationic cellulose derivatives, mention may be made ofquaternized cellulose ether derivatives, such as those described inapplication EP-A-0,189,935, and in particular the polymer marketed underthe name “Quatrisoft LM 200” by the company Union Carbide; thesepolymers are also defined in the CTFA dictionary (5th edition, 1993) ashydroxyethylcellulose quaternary ammoniums which have been reacted withan epoxide substituted with a lauryldimethylammonium group and arelisted therein under the name “Polyquaternium 24”.

[0050] Among the substantive polymers of themethacryloyloxyethyltrimethylammonium halide polymer type which can beused according to the invention, mention may be made in particular ofthe products referred to in the CTFA dictionary (5th edition, 1993) as“Polyquaternium 37”, “Polyquaternium 32” and “Polyquaternium 35”, whichcorrespond respectively, as regards “Polyquaternium 37”, to crosslinkedpoly(methacryloyloxyethyltrimethylammonium chloride), as a 50%dispersion in mineral oil, sold under the name Salcare SC95 by thecompany Allied Colloids, as regards “Polyquaternium 32”, to thecrosslinked copolymer of acrylamide and ofmethacryloyloxyethyltrimethylammonium chloride (20/80 by weight), as a50% dispersion in mineral oil, sold under the name Salcare SC92 by thecompany Allied Colloids, and, as regards “Polyquaternium 35”, to themethosulphate of the copolymer of methacryloyloxyethyltrimethylammoniumand of methacryloyloxyethyldimethylacetylammonium, sold under the namePlex 7525L by the company Rohm GmbH.

[0051] Among the substantive polymers of dimethyldiallylammonium halidetype which may be used according to the invention, mention may be madein particular of:

[0052] dimethyldiallylammonium chloride homopolymers, such as the onesold under the name “Merquat 100” by the company Merck;

[0053] copolymers of dimethyldiallylammonium chloride and of acrylicacid, such as the one in proportions of 80/20 by weight sold under thename Merquat 280 by the company Calgon.

[0054] Among the substantive polymers of the poly-quaternary ammoniumtype which can be used according to the invention, mention may be madein particular of:

[0055] the polymers prepared and described in French patent 2,270,846,consisting of repeating units corresponding to formula (I) below:

[0056] and in particular those in which the molecular weight, determinedby gel permeation chromatography, is between 9500 and 9900;

[0057] the polymers prepared and described in French patent 2,270,846,consisting of repeating units corresponding to formula (II) below:

[0058] and in particular those in which the molecular weight, determinedby gel permeation chromatography, is about 1200;

[0059] the polymers described and prepared in U.S. Pat. Nos. 4,157,388,4,390,689, 4,702,906 and 4,719,282 and consisting of repeating unitscorresponding to formula (III) below:

[0060] in which p denotes an integer ranging from 1 to 6 approximately,D can be zero or can represent a group —(CH₂)_(r)—CO— in which r denotesa number equal to 4 or 7, and in particular those in which the molecularmass is less than 100,000, preferably less than or equal to 50,000; suchpolymers are sold in particular by the company Miranol under the names“Mirapol A15”, “Mirapol AD1”, “Mirapol AZ1” and “Mirapol 175”.

[0061] Among the vinylpyrrolidone polymers (PVP) containing cationicunits which can be used in accordance with the invention, mention may bemade in particular of:

[0062] a) vinylpyrrolidone polymers containing dimethylamino-ethylmethacrylate units; among these, mention may be made of:

[0063] the vinylpyrrolidone/dimethylaminoethyl meth-acrylate (20/80 byweight) copolymer sold under the trade name Copolymer 845 by the companyISP,

[0064] the vinylpyrrolidone/dimethylaminoethyl meth-acrylate copolymersquaternized with diethyl sulphate, sold under the names Gafquat 734,755, 755 S and 755 L by the company ISP,

[0065] the PVP/dimethylaminoethyl methacrylate-/hydrophilic polyurethanecopolymers sold under the trade name Pecogel GC-310 by the company UCIBor alternatively under the names Aquamere C 1031 and C 1511 by thecompany Blagden Chemicals,

[0066] the quaternized or non-quaternized PVP/dimethylaminoethylmethacrylate/C8 to C16 olefin copolymers sold under the names Ganex ACP1050 to 1057, 1062 to 1069 and 1079 to 1086 by the company ISP,

[0067] the PVP/dimethylaminoethyl methacrylate-/vinylcaprolactamcopolymer sold under the name Gaffix VC 713 by the company ISP.

[0068] b) vinylpyrrolidone polymers containingmethacrylamido-propyltrimethylammonium (MAPTAC) units, among whichmention may be made in particular of:

[0069] the vinylpyrrolidone/MAPTAC copolymers sold under the trade namesGafquat ACP 1011 and Gafquat HS 100 by the company ISP,

[0070] c) vinylpyrrolidone polymers containing methylvinyl-imidazoliumunits, and among which mention may be made more particularly of:

[0071] the PVP/methylvinylimidazolium chloride copolymers sold under thenames Luviquat FC 370, FC 550, FC 905 and HM 552 by the company BASF,

[0072] the PVP/methylvinylimidazolium chloride-/vinylimidazole copolymersold under the name Luviquat 8155 by the company BASF,

[0073] the PVP/methylvinylimidazolium methosulphate copolymer sold underthe name Luviquat MS 370 by the company BASF.

[0074] The concentration of substantive polymer can range between 0.01and 10% approximately relative to the total weight of the dyecomposition applied to the hair, and preferably between 0.1 and 5%.

[0075] A subject of the present invention is also a ready-to-usecomposition for the oxidation dyeing of keratin fibres, and inparticular human keratin fibres such as the hair, of the typecomprising, in a medium which is suitable for dyeing, at least oneoxidation base and, where appropriate, one or more couplers, which ischaracterized in that it contains:

[0076] (a) at least one enzyme of 2-electron oxidoreductase type in thepresence of at least one donor for the said enzyme;

[0077] (b) at least one substantive polymer chosen from the groupconsisting of:

[0078] (i) cationic cellulose derivatives;

[0079] (ii) dimethyldiallylammonium halide homopolymers and copolymersof dimethyldiallylammonium halide and of (meth)acrylic acid;

[0080] (iii) methacryloyloxyethyltrimethylammonium halide homopolymersand copolymers;

[0081] (iv) polyquaternary ammonium polymers;

[0082] (v) vinylpyrrolidone polymers containing cationic units;

[0083] (vi) mixtures thereof.

[0084] The nature of the oxidation base(s) used in the ready-to-use dyecomposition is not a critical factor. They can be chosen, in particular,from para-phenylenediamines, double bases, para-aminophenols,ortho-aminophenols and heterocyclic oxidation bases.

[0085] Among the para-phenylenediamines which can be used as oxidationbases in the dye compositions in accordance with the invention, mentionmay be made in particular of the compounds of formula (IV) below, andthe addition salts thereof with an acid:

[0086] in which:

[0087] R₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ poly-hydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ alkyl radical substitutedwith a nitrogenous group, a phenyl radical or a 4′-amino-phenyl radical;

[0088] R₂ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ poly-hydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedwith a nitrogenous group;

[0089] R₃ represents a hydrogen atom, a halogen atom such as a chlorine,bromine, iodine or fluorine atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₁-C₄ hydroxyalkoxy radical, anacetylamino(C_(l)-C₄)alkoxy radical, a C₁-C₄ mesylamino-alkoxy radicalor a carbamoylamino(C_(l)-C₄)alkoxy radical,

[0090] R₄ represents a hydrogen or halogen atom or a C₁-C₄ alkylradical.

[0091] Among the nitrogenous groups of formula (IV) above, mention maybe made in particular of amino, mono(C₁-C₄)alkylamino,di(C₁-C₄)alkylamino, tri(C₁-C₄)-alkylamino,monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium radicals.

[0092] Among the para-phenylenediamines of formula (IV) above, mentionmay be made more particularly of para-phenylenediamine,para-toluylenediamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylene-diamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(P-hydroxyethyl)-2-methylaniline,4-amino-2-chloro-N,N-bis(β-hydroxyethyl)aniline,2-β-hydroxy-ethyl-para-phenylenediamine,2-fluoro-para-phenylene-diamine, 2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxy-methyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl) -para-phenylenediamine,N-(4′-aminophenyl)-para-phenylene-diamine,N-phenyl-para-phenylenediamine,2-β-hydroxy-ethyloxy-para-phenylenediamine,2-β-acetylamino-ethyloxy-para-phenylenediamine andN-(β-methoxyethyl)-para-phenylenediamine, and the addition salts thereofwith an acid.

[0093] Among the para-phenylenediamines of formula (IV) above,para-phenylenediamine, para-toluylene-diamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxy-ethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxy-ethyl)-para-phenylenediamine,2-chloro-para-phenylene-diamine and2-β-acetylaminoethyloxy-para-phenylene-diamine and the addition saltsthereof with an acid are most particularly preferred.

[0094] According to the invention, the term double bases is understoodto refer to the compounds containing at least two aromatic rings bearingamino and/or hydroxyl groups.

[0095] Among the double bases which can be used as oxidation bases inthe dye compositions in accordance with the invention, mention may bemade in particular of the compounds corresponding to formula (V) below,and the addition salts thereof with an acid:

[0096] in which

[0097] Z₁ and Z₂, which may be identical or different, represent ahydroxyl or —NH₂ radical which may be substituted with a C₁-C₄ alkylradical or with a linker arm Y;

[0098] the linker arm Y represents a linear or branched alkylene chaincontaining from 1 to 14 carbon atoms, which may be interrupted by orterminated with one or more nitrogenous groups and/or one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, and optionallysubstituted with one or more hydroxyl or C₁-C₄ alkoxy radicals;

[0099] R₅ and R₆ represent a hydrogen or halogen atom, a C₁-C₄ alkylradical, a C_(l)-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ aminoalkyl radical or a linker arm Y;

[0100] R₇, R₈, R₉, R₁₀, R₁₁ and R₁₂, which may be identical ordifferent, represent a hydrogen atom, a linker arm Y or a C₁-C₄ alkylradical;

[0101] it being understood that the compounds of formula (V) containonly one linker arm Y per molecule.

[0102] Among the nitrogenous groups of formula (V) above, mention may bemade in particular of amino, mono (C₁-C₄) alkylamino,di(C_(l)-C₄)alkylamino, tri(C₁-C₄)alkylamino,monohydroxy(C₁-C₄)alkylamino, imidazo-linium and ammonium radicals.

[0103] Among the double bases of formula (V) above, mention may be mademore particularly ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopro-panol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-amino-phenyl)ethylenediamine,N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis-(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenedi-amine and1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition saltsthereof with an acid.

[0104] Among these double bases of formula (V),N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-di-aminopropanoland 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of the additionsalts thereof with an acid, are particularly preferred.

[0105] Among the para-aminophenols which can be used as oxidation basesin the dye compositions in accordance with the invention, mention may bemade in particular of the compounds corresponding to formula (VI) below,and the addition salts thereof with an acid:

[0106] in which:

[0107] R₁₃ represents a hydrogen or halogen atom or a C₁-C₄ alkyl,C_(l)-C₄ monohydroxyalkyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl, C₁-C₄ aminoalkylor hydroxy(C₁-C₄)alkylamino(C₁-C₄)alkyl radical,

[0108] R₁₄ represents a hydrogen or halogen atom or a C₁-C₄-alkyl, C₁-C₄monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, C_(l)-C₄ aminoalkyl, C₁-C₄cyanoalkyl or (C₁-C₄)alkoxy-(C₁-C₄)alkyl radical,

[0109] it being understood that at least one of the radicals R₁₃ or R₁₄represents a hydrogen atom.

[0110] Among the para-aminophenols of formula (VI) above, mention may bemade more particularly of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and the addition salts thereof with an acid.

[0111] Among the ortho-aminophenols which can be used as oxidation basesin the dye compositions in accordance with the invention, mention may bemade more particularly of 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the additionsalts thereof with an acid.

[0112] Among the heterocyclic bases which can be used as oxidation basesin the dye compositions in accordance with the invention, mention may bemade more particularly of pyridine derivatives, pyrimidine derivatives,pyrazole derivatives and pyrazolo-pyrimidine derivatives, and theaddition salts thereof with an acid.

[0113] Among the pyridine derivatives, mention may be made moreparticularly of the compounds described, for example, in patents GB1,026,978 and GB 1,153,196, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and3,4-diaminopyridine, and the addition salts thereof with an acid.

[0114] Among the pyrimidine derivatives, mention may be made moreparticularly of the compounds described, for example, in German patentDE 2,359,399 or Japanese patent JP 88-169,571 or patent application WO96/15765, such as 2,4,5,6-tetraaminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-pyrimidine, andthe addition salts thereof with an acid.

[0115] Among the pyrazole derivatives, mention may be made moreparticularly of the compounds described in patents DE 3,843,892, DE4,133,957 and patent applications WO 94/08969, WO 94/08970,FR-A-2,733,749 and DE 195 43 988, such as 4,5-diamino-1-methyl-pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethyl-pyrazole,4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-di-methyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methyl-pyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-iso-propylpyrazole,4,5-diamino-3-methyl-1-isopropyl-pyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-tri-aminopyrazole,3,5-diamino-1-methyl-4-methylamino-pyrazole and3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the additionsalts thereof with an acid.

[0116] Among the pyrazolopyrimidine derivatives, mention may be mademore particularly of the pyrazolo[1,5-a]pyrimidines of formula (VII)below, and the addition salts thereof with an acid or with a base andthe tautomeric forms thereof, when a tautomeric equilibrium exists:

[0117] in which:

[0118] R₁₅, R₁₆, R₁₇ and R₁₈, which may be identical or different,denote a hydrogen atom, a C₁-C₄ alkyl radical, an aryl radial, a C₁-C₄hydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ aminoalkyl radical (it beingpossible for the amine to be protected with an acetyl, ureido orsulphonyl radical), a (C₁-C₄)alkylamino(C₁-C₄)alkyl radical, adi[(C_(l)-C₄)alkyl]amino(C₁-C₄)alkyl radical (it being possible for thedialkyl radicals to form a 5- or 6-membered carbon-based ring or aheterocycle), a hydroxy(C₁-C₄)alkyl- or di[hydroxy(C₁-C₄)alkyl]amino(C₁-C₄) alkyl radical;

[0119] the radicals X, which may be identical or different, denote ahydrogen atom, a C₁-C₄ alkyl radical, an aryl radical, a C₁-C₄hydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a C₁-C₄aminoalkyl radical, a (C₁-C₄)alkylamino(C₁-C₄)alkyl radical, adi[(C₁-C₄)alkyl]amino(C₁-C₄)alkyl radical (it being possible for thedialkyls to form a 5- or 6-membered carbon-based ring or a heterocycle),a hydroxy(C_(l)-C₄)alkyl- or di-[hydroxy(C₁-C₄)alkyl]amino(C₁-C₄)alkylradical, an amino radical, a (C₁-C₄)alkyl- or di[(C₁-C₄)alkyl]aminoradical; a halogen atom, a carboxylic acid group, a sulphonic acidgroup;

[0120] i is equal to 0, 1, 2 or 3;

[0121] p is equal to 0 or 1;

[0122] q is equal to 0 or 1;

[0123] n is equal to 0 or 1;

[0124] with the proviso that:

[0125] the sum p+q is other than 0;

[0126] when p+q is equal to 2, then n is equal to 0 and the groupsNR₁₅R₁₆ and NR₁₇R₁₈ occupy the (2,3); (5,6);

[0127] (6,7); (3,5) or (3,7) positions;

[0128] when p +q is equal to 1, then n is equal to 1 and the groupNR₁₅R₁₆ (or NR₁₇R₁₈) and the OH group occupy the (2,3); (5,6); (6,7);(3,5) or (3,7) positions.

[0129] When the pyrazolo[1,5-a]pyrimidines of formula (VII) above aresuch that they contain a hydroxyl group on one of the positions 2, 5 or7 α to a nitrogen atom, a tautomeric equilibrium exists represented, forexample, by the following scheme:

[0130] Among the pyrazolo[l,5-a]pyrimidines of formula (VII) above,mention may be made in particular of:

[0131] pyrazolo[1,5-a]pyrimidine-3,7-diamine;

[0132] 2,5-dimethylpyrazolo[1,5-a]pyrimidimine-3,7-diamine;

[0133] pyrazolo[1,5-a]pyrimidine-3,5-diamine;

[0134] 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;

[0135] 3-aminopyrazolo[1,5-a]pyrimidin-7-ol;

[0136] 3-aminopyrazolo[1,5-a]pyrimidin-5-ol;

[0137] 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;

[0138] 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;

[0139]2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]ethanol;

[0140]2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)amino]ethanol;

[0141] 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

[0142] 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

[0143] 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

[0144] and the addition salts thereof and the tautomeric forms thereof,when a tautomeric equilibrium exists.

[0145] The pyrazolo[1,5-a]pyrimidines of formula (VII) above can beprepared by cyclization starting with an aminopyrazole, according to thesyntheses described in the following references:

[0146] EP 628559 Beiersdorf-Lilly.

[0147] R. Vishdu, H. Navedul, Indian J. Chem., 34b (6), 514, 1995.

[0148] N. S. Ibrahim, K. U. Sadek, F. A. Abdel-Al, Arch. Pharm., 320,240, 1987.

[0149] R. H. Springer, M. B. Scholten, D. E. O'Brien, T. Novinson, J. P.Miller, R. K. Robins, J. Med. Chem., 25, 235, 1982.

[0150] T. Novinson, R. K. Robins, T. R. Matthews, J. Med. Chem., 20,296, 1977.

[0151] U.S. Pat. No. 3,907,799 ICN Pharmaceuticals.

[0152] The pyrazolo[1,5-a]pyrimidines of formula (VII) above can also beprepared by cyclization starting from hydrazine, according to thesyntheses described in the following references:

[0153] A. McKillop and R. J. Kobilecki, Heterocycles, 6(9), 1355, 1977.

[0154] E. Alcade, J. De Mendoza, J. M. Marcia-Marquina, C. Almera, J.Elguero, J. Heterocyclic Chem., 11(3), 423, 1974.

[0155] K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc.Japan, 47(2), 476, 1974.

[0156] The oxidation base(s) in accordance with the invention preferablyrepresent(s) from 0.0005 to 12% by weight approximately relative to thetotal weight of the ready-to-use dye composition, and even morepreferably from 0.005 to 6% by weight approximately relative to thisweight.

[0157] The couplers which can be used are those used conventionally inoxidation dye compositions, i.e. meta-phenylenediamines,meta-aminophenols and meta-diphenols, mono- or polyhydroxylatednaphthalene derivatives, sesamol and its derivatives and heterocycliccompounds such as, for example, indole derivatives, indolinederivatives, benzimidazole derivatives, benzomorpholine derivatives,sesamol derivatives, pyrazoloazole derivatives, pyrroloazolederivatives, imidazoloazole derivatives, pyrazolo-pyrimidinederivatives, pyrazoline-3,5-dione derivatives, pyrrolo[3,2-d]oxazolederivatives, pyrazolo[3,4-d]thiazole derivatives, thiazoloazole S-oxidederivatives and thiazoloazole S,S-dioxide derivatives, and the additionsalts thereof with an acid.

[0158] These couplers can be chosen in particular from2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol,3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxy-benzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, a-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and theaddition salts thereof with an acid.

[0159] When they are present, these couplers preferably represent from0.0001 to 10% by weight approximately relative to the total weight ofthe ready-to-use dye composition, and even more preferably from 0.005 to5% by weight approximately relative to this weight.

[0160] In general, the addition salts with an acid which can be used inthe context of the dye compositions of the invention (oxidation basesand couplers) are chosen in particular from the hydrochlorides,hydrobromides, sulphates, tartrates, lactates and acetates.

[0161] The dye composition of the invention can also contain, inaddition to the oxidation dye precursors defined above and the optionalcombined couplers, direct dyes to enrich the shades with glints. Thesedirect dyes can thus be chosen in particular from nitro dyes, azo dyesor anthraquinone dyes.

[0162] The subject of the invention is also a process for dyeing keratinfibres, and in particular human keratin fibres such as the hair, usingthe ready-to-use dye composition as defined above.

[0163] According to this process, at least one ready-to-use dyecomposition as defined above is placed on the fibres, for a period whichis sufficient to develop the desired coloration, after which the fibresare rinsed, optionally washed with shampoo, rinsed again and dried.

[0164] The time required to develop the coloration on the keratin fibresis generally between 3 and 60 minutes and even more precisely between 5and 40 minutes.

[0165] According to a specific embodiment of the invention, the processincludes a first step which consists in separately storing, on the onehand, a composition (A) comprising, in a medium which is suitable fordyeing, at least one oxidation base and optionally at least one coupleras defined above, and, on the other hand, a composition (B) containing,in a medium which is suitable for dyeing, at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme and at least one substantive polymer as defined above,and then in mixing them together at the time of use, before applyingthis mixture to the keratin fibres.

[0166] According to another specific embodiment of the invention, thesubstantive polymer is incorporated into composition (A).

[0167] Another subject of the invention is a multi-compartment dyeingdevice or “kit” or any other multi-compartment packaging system, a firstcompartment of which contains composition (A) as defined above and asecond compartment of which contains composition (B) as defined above.These devices can be equipped with means for applying the desiredmixture to the hair, such as the devices described in patentFR-2,586,913 in the name of the Applicant.

[0168] A subject of the present invention is also a novel process fortreating keratin substances, in particular the hair, in order to obtaina permanent reshaping of this hair, in particular in the form ofpermanent-waved hair, this process comprising the following steps: (i) areducing composition is applied to the keratin substance to be treated,the keratin substance being placed under mechanical tension before,during or after the said application, (ii) the keratin substance isoptionally rinsed, (iii) an oxidizing composition as defined above isapplied to the optionally rinsed keratin substance, (iv) the keratinsubstance is optionally rinsed again.

[0169] The first step (i) of this process consists in applying areducing composition to the hair. This application is carried out lockby lock or all at once.

[0170] The reducing composition comprises, for example, at least onereducing agent, which can be chosen in particular from thioglycolicacid, cysteine, cysteamine, glyceryl thioglycolate, thiolactic acid orthiolactic or thioglycolic acid salts.

[0171] The usual step for placing the hair under tension in a shapecorresponding to the desired final shape for this hair (for examplecurls) can be carried out by any suitable means, in particularmechanical means, known per se for maintaining the hair under tension,such as, for example, rollers, curlers and the like.

[0172] The hair can also be shaped without the aid of external means,simply with the fingers.

[0173] Before carrying out the following optional rinsing step (ii), thehair onto which the reducing composition has been applied should,conventionally, be left to stand for a few minutes, generally between 5minutes and one hour, preferably between 10 and 30 minutes, so as togive the reducing agent enough time to act correctly on the hair. Thiswaiting phase preferably takes place at a temperature ranging from 35°C. to 45° C., while preferably also protecting the hair with a hood.

[0174] In the optional second step of the process (step (ii)), the hairimpregnated with the reducing composition is then rinsed thoroughly withan aqueous composition.

[0175] Next, in a third step (step (iii)), the oxidizing composition ofthe invention is applied to the hair thus rinsed, with the aim of fixingthe new shape given to the hair.

[0176] As in the case of the application of the reducing composition,the hair onto which the oxidizing composition has been applied is then,conventionally, left for a standing or waiting phase lasting a fewminutes, generally between 3 and 30 minutes, preferably between 5 and 15minutes.

[0177] If the hair was maintained under tension by external means, thesemeans (rollers, curlers or the like) can be removed from the hair beforeor after the fixing step.

[0178] Lastly, in the final step of the process according to theinvention (step (iv)), which is also optional, the hair impregnated withthe oxidizing composition is rinsed thoroughly, generally with water.

[0179] Hair which is soft and easy to disentangle is finally obtained.The hair is wavy.

[0180] The oxidizing composition according to the invention can also beused in a process for bleaching keratin fibres, and in particular thehair.

[0181] The bleaching process according to the invention comprises a stepof applying an oxidizing composition according to the invention to thekeratin fibres in the presence or absence of an auxiliary oxidizingagent. Conventionally, a second step of the bleaching process accordingto the invention is a step of rinsing the keratin fibres.

[0182] The medium which is suitable for the keratin fibres (or thesupport) for the ready-to-use dye compositions and for the oxidizingcompositions used for the permanent reshaping or bleaching of keratinfibres in accordance with the invention generally consists of water orof a mixture of water and at least one organic solvent in order todissolve the compounds which would not be sufficiently soluble in water.By way of organic solvent, mention may be made, for example, of C₁-C₄alkanols such as ethanol and isopropanol; glycerol; glycols and glycolethers such as 2-butoxyethanol, propylene glycol, propylene glycolmonomethyl ether, diethylene glycol monoethyl ether and monomethylether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol,similar products and mixtures thereof.

[0183] The solvents can be present in proportions preferably of between1 and 40% by weight approximately relative to the total weight of thedye composition, and even more preferably between 5 and 30% by weightapproximately.

[0184] The pH of the ready-to-use dye compositions and of the oxidizingcompositions used for the permanent reshaping or bleaching of thekeratin fibres in accordance with the invention is chosen such that theenzymatic activity of the 2-electron oxidoreductase is not adverselyaffected. It is generally between 5 and 11 approximately, and preferablybetween 6.5 and 10 approximately. It can be adjusted to the desiredvalue using acidifying or basifying agents usually used for dyeingkeratin fibres.

[0185] Among the acidifying agents, mention may be made, by way ofexample, of inorganic or organic acids such as hydrochloric acid,orthophosphoric acid, sulphuric acid, carboxylic acids such as aceticacid, tartaric acid, citric acid or lactic acid, and sulphonic acids.

[0186] Among the basifying agents, mention may be made, by way ofexample, of aqueous ammonia, alkaline carbonates, alkanolamines such asmono-, di- and triethanolamines, 2-methyl-2-aminopropanol andderivatives thereof, sodium hydroxide, potassium hydroxide and thecompounds of formula (VIII) below:

[0187] in which W is a propylene residue optionally substituted with ahydroxyl group or a C₁-C₄ alkyl radical; R₁₉, R₂₀, R₂₁ and R₂₂, whichmay be identical or different, represent a hydrogen atom or a C_(l)-C₄alkyl or C₁-C₄ hydroxyalkyl radical.

[0188] The ready-to-use dye compositions and the oxidizing compositionsfor permanently reshaping or bleaching keratin fibres in accordance withthe invention can also contain various adjuvants used conventionally incompositions for the dyeing, permanent reshaping or bleaching of thehair, such as anionic, cationic, nonionic, amphoteric or zwitterionicsurfactants or mixtures thereof, anionic or nonionic polymers, inorganicor organic thickeners, anti-oxidants, enzymes other than the 2-electronoxido-reductases used in accordance with the invention, such as, forexample, peroxidases, penetration agents, sequestering agents,fragrances, buffers, dispersing agents, conditioners such as, forexample, silicones, film-forming agents, preserving agents andopacifiers.

[0189] Needless to say, a person skilled in the art will take care toselect this or these optional complementary compound(s) such that theadvantageous properties intrinsically associated with the compositionsin accordance with the invention are not, or are not substantially,adversely affected by the addition or additions envisaged.

[0190] The ready-to-use dye compositions and the oxidizing compositionsused for the permanent reshaping or bleaching of keratin fibres inaccordance with the invention can be in various forms, such as in theform of liquids, creams or gels, which are optionally pressurized, or inany other form which is suitable for dyeing, permanently reshaping orbleaching keratin fibres, and in particular human hair.

[0191] In the case of a ready-to-use dye composition, the oxidationdyes(s) and the 2-electron oxido-reductase(s) are present in the saidcomposition, which must be free of oxygen gas, so as to avoid anypremature oxidation of the oxidation dye(s).

[0192] Concrete examples illustrating the invention will now be given.

[0193] In the text hereinabove and hereinbelow, except where otherwisementioned, the percentages are expressed on a weight basis.

[0194] The examples which follow illustrate the invention without beinglimiting in nature.

EXAMPLES 1 AND 2 OF DYE COMPOSITIONS

[0195] The ready-to-use dye compositions below were prepared (contentsin grams):

EXAMPLE 1

[0196] Uricase from Arthrobacter globiformis 1.5 g at a concentration of20 International Units (I.U.)/mg, sold by the company Sigma Uric acid1.5 g Para-phenylenediamine 0.324 g Resorcinol 0.33 g Polyquaternaryammonium of formula (I) 1.0 g A.M. [tetramethylhexamethylenediaminedi-chloro-4β-propylenediamine polycon- densate as an aqueous 60% solution]Distilled water qs 100 g

EXAMPLE 2

[0197] Uricase from Arthrobacter globiformis 1.5 g at a concentration of20 International Units (I.U.)/mg, sold by the company Sigma Uric acid1.5 g Para-phenylenediamine 0.324 g Resorcinol 0.33 gDimethyldiallylammonium chloride-/ 1.0 g A.M. acrylic acid copolymer asan aqueous 40.5% solution, sold under the name Merquat 280 by CalgonDistilled water qs 100 g

[0198] Each of the ready-to-use dye compositions described above wasapplied to locks of natural grey hair containing 90% white hairs for 30minutes. The hair was then rinsed, washed with a standard shampoo andthen dried.

[0199] Locks of hair dyed a matt dark-blond colour were obtained witheach of the dye compositions.

EXAMPLE 3 Oxidizing Composition for Permanent-Waving or Bleaching

[0200] Uricase from Arthrobacter globiformis 1.8 g at a concentration of20 International Units (I.U.)/mg, sold by the company Sigma Uric acid1.65 g Ethanol 20.0 g (C₈-C₁₀) alkyl polyglucoside as an 8.0 g aqueoussolution containing 60% active material (A.M.), sold under the nameOramix CG110 by the company SEPPIC Dimethyldiallylammonium chloridehomo- 1.0 g A.M. polymer as an aqueous 40% solution, sold under the nameMerquat 100 by Calgon 2-Methyl-2-amino-1-propanol qs pH 9.5 Distilledwater qs 100 g

1. Cosmetic and/or dermatological composition intended for treatingkeratin fibres, in particular human keratin fibres and more particularlyhuman hair, comprising, in a support which is suitable for keratinfibres: (a) at least one enzyme of 2-electron oxidoreductase type in thepresence of at least one donor for the said enzyme; (b) at least onesubstantive polymer chosen from the group consisting of: (i) cationiccellulose derivatives; (ii) dimethyldiallylammonium halide, homopolymersand copolymers of dimethyldiallylammonium halide and of (meth)acrylicacid; (iii) methacryloyloxyethyltrimethylammonium halide homopolymersand copolymers; (iv) polyquaternary ammonium polymers; (v)vinylpyrrolidone polymers containing cationic units; (vi) mixturesthereof.
 2. Composition according to claim 1, characterized in that the2-electron oxidoreductase is chosen from uricases of animal,microbiological or biotechnological origin.
 3. Composition according toclaim 1 or 2, characterized in that the 2-electron oxidoreductase(s)represent(s) from 0.01 to 20% by weight relative to the total weight ofthe composition.
 4. Composition according to claim 3, characterized inthat the 2-electron oxidoreductase(s) represent(s) from 0.1 to 5% byweight relative to the total weight of the composition.
 5. Compositionaccording to claim 2, characterized in that the donor (or substrate) forthe said 2-electron oxidoreductase is chosen from uric acid and itssalts.
 6. Composition according to any one of the preceding claims,characterized in that the donor(s) represent(s) from 0.01 to 20% byweight relative to the total weight of the composition.
 7. Compositionaccording to claim 6, characterized in that the donor(s) represent(s)from 0.1 to 5% by weight relative to the total weight of thecomposition.
 8. Composition according to any one of claims 1 to 7,characterized in that the cellulosic substantive polymers arequaternized cellulose ether derivatives.
 9. Composition according to anyone of claims 1 to 7, characterized in that the substantive polymers ofdimethyldiallylammonium halide polymer or copolymer type are chosenfrom: the crosslinked poly(methacryloyloxyethyltrimethyl-ammoniumchloride) homopolymers, as a 50% dispersion in mineral oil, thecrosslinked copolymer of acrylamide and ofmethacryloyloxyethyltrimethylammonium chloride (20/80 by weight), as a50% dispersion in mineral oil, the methosulphate of the copolymer ofmeth-acryloyloxyethyltrimethylammonium and ofmeth-acryloyloxyethyldimethylacetylammonium.
 10. Composition accordingto any one of claims 1 to 7, characterized in that the substantivepolymers of the dimethyldiallylammonium halide polymer type are chosenfrom: dimethyldiallylammonium chloride homopolymers, the copolymer ofdimethyldiallylammonium chloride and of acrylic acid.
 11. Compositionaccording to any one of claims 1 to 7, characterized in that thesubstantive polymers of the polyquaternary ammonium type are chosenfrom: polymers consisting of repeating units corresponding to formula(I) below:

polymers consisting of repeating units corresponding to formula (II)below:

polymers consisting of repeating units corresponding to formula (III)below:

in which p denotes an integer ranging from 1 to 6 approximately, D canbe zero or can represent a group —(CH₂)_(r)—CO— in which r denotes anumber equal to 4 or to
 7. 12. Composition according to any one ofclaims 1 to 7, characterized in that the substantive polymers of thevinylpyrrolidone polymer type containing cationic units are chosen from:a) vinylpyrrolidone polymers containing dimethylamino-ethyl methacrylateunits; b) vinylpyrrolidone polymers containingmethacrylamido-propyltrimethylammonium units; c) vinylpyrrolidonepolymers containing methylvinyl-imidazolium units.
 13. Compositionaccording to any one of claims 1 to 12, characterized in that theconcentration of substantive polymer can range between 0.01 and 10%relative to the total weight of the composition, and preferably between0.1 and 5%.
 14. Ready-to-use composition according to any one of claims1 to 13, for the oxidation dyeing of keratin fibres, and in particularhuman keratin fibres such as the hair, of the type also comprising, in amedium which is suitable for keratin fibres, at least one oxidation baseand, optionally, one or more couplers.
 15. Composition according toclaim 14, characterized in that the oxidation bases are chosen frompara-phenylenediamines, double bases, ortho- or para-aminophenols andheterocyclic bases, as well as the addition salts of these compoundswith an acid.
 16. Composition according to claim 14 or 15, characterizedin that the oxidation bases are present in concentrations ranging from0.0005 to 12% by weight relative to the total weight of the composition.17. Composition according to any one of claims 14 to 16, characterizedin that the couplers are chosen from meta-phenylenediamines,meta-aminophenols, meta-diphenols and heterocyclic couplers, and theaddition salts of these compounds with an acid.
 18. Compositionaccording to any one of claims 14 to 17, characterized in that thecouplers are present in concentrations ranging from 0.0001 to 10% byweight relative to the total weight of the composition.
 19. Compositionaccording to any one of claims 14 to 18, characterized in that theaddition salts with an acid for the oxidation bases and the couplers arechosen from the hydrochlorides, hydrobromides, sulphates, tartrates,lactates and acetates.
 20. Composition according to any one of claims 14to 19, characterized in that it also contains direct dyes. 21.Composition according to any one of claims 1 to 20, characterized inthat the medium which is suitable for the keratin fibres (or support)consists of water or of a mixture of water and at least one organicsolvent.
 22. Composition according to any one of claims 1 to 21,characterized in that the organic solvents can be present in proportionspreferably ranging from 1 to 40% by weight relative to the total weightof the composition, and even more preferably ranging from 5 to 30% byweight.
 23. Composition according to any one of claims 1 to 24,characterized in that the pH ranges from 5 to 11 and preferably from 6.5to
 10. 24. Composition according to any one of claims 1 to 23,characterized in that it also contains at least one cosmetic adjuvantused conventionally in compositions for dyeing, permanently reshaping orbleaching the hair, chosen from the group consisting of anionic,cationic, nonionic, amphoteric or zwitterionic surfactants or mixturesthereof, anionic or nonionic polymers, inorganic or organic thickeners,anti-oxidants, enzymes other than the 2-electron oxido-reductases,penetration agents, sequestering agents, fragrances, buffers, dispersingagents, conditioners, film-forming agents, preserving agents andopacifiers.
 25. Process for dyeing keratin fibres, and in particularhuman keratin fibres such as the hair, characterized in that at leastone ready-to-use dye composition as defined in any one of claims 14 to24 is placed on the said fibres for a period which is sufficient todevelop the desired coloration.
 26. Process according to claim 25,characterized in that it includes a first step which consists inseparately storing, on the one hand, a composition (A) comprising, in amedium which is suitable for dyeing, at least one oxidation base andoptionally at least one coupler as defined in any one of claims 14 to19, and, on the other hand, a composition (B) containing, in a mediumwhich is suitable for the keratin fibres, at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme as defined in any one of the preceding claims, and thenin mixing them together at the time of use, before applying this mixtureto the keratin fibres; composition (A) or composition (B) containing thesubstantive polymer as defined in the preceding claims. 27.Multi-compartment dyeing device or “kit”, characterized in that itcontains a first compartment containing composition (A) as defined inclaim 26 and a second compartment containing composition (B) as definedin claim
 26. 28. Process for treating keratin fibres, in particular thehair, in order to obtain a permanent reshaping of this hair, inparticular in the form of permanent-waved hair, this process comprisingthe following steps: (i) a reducing composition is applied to thekeratin fibres to be treated, the keratin substance being placed undermechanical tension before, during or after the said application, (ii)the keratin substance is optionally rinsed, (iii) an oxidizingcomposition as defined in any one of claims 1 to 13 and 21 to 24 isapplied to the optionally rinsed keratin substance, (iv) the keratinsubstance is optionally rinsed again.
 29. Process for treating keratinfibres, in particular the hair, in order to bleach them, this processcomprising the application of an oxidizing composition as defined in anyone of claims 1 to 13 and 21 to 24 optionally containing an auxiliaryoxidizing agent and a second step of rinsing the keratin fibres.